JPH056909A - Silver-glass paste - Google Patents

Silver-glass paste

Info

Publication number
JPH056909A
JPH056909A JP3027411A JP2741191A JPH056909A JP H056909 A JPH056909 A JP H056909A JP 3027411 A JP3027411 A JP 3027411A JP 2741191 A JP2741191 A JP 2741191A JP H056909 A JPH056909 A JP H056909A
Authority
JP
Japan
Prior art keywords
paste
silver
glass
resinate
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP3027411A
Other languages
Japanese (ja)
Inventor
My N Nguyen
エヌ．ヌグイエン マイ
Mark A Blocker
エイ．ブロツカー マーク
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JOHNSON MATTHEY Inc
Original Assignee
JOHNSON MATTHEY Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JOHNSON MATTHEY Inc filed Critical JOHNSON MATTHEY Inc
Publication of JPH056909A publication Critical patent/JPH056909A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
    • H01L23/49883—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials the conductive materials containing organic materials or pastes, e.g. for thick films
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/291—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29101—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of less than 400°C
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29199—Material of the matrix
    • H01L2224/29286—Material of the matrix with a principal constituent of the material being a non metallic, non metalloid inorganic material
    • H01L2224/29288—Glasses, e.g. amorphous oxides, nitrides or fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/29339—Silver [Ag] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H01L2224/8384—Sintering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H01L2224/8389—Bonding techniques using an inorganic non metallic glass type adhesive, e.g. solder glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01005—Boron [B]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01006—Carbon [C]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01011—Sodium [Na]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01012—Magnesium [Mg]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01014—Silicon [Si]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01015—Phosphorus [P]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/0102—Calcium [Ca]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01027—Cobalt [Co]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01033—Arsenic [As]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01045—Rhodium [Rh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01046—Palladium [Pd]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01047—Silver [Ag]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01056—Barium [Ba]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01077—Iridium [Ir]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01082—Lead [Pb]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/013—Alloys
    • H01L2924/014—Solder alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/078—Adhesive characteristics other than chemical
    • H01L2924/0781—Adhesive characteristics other than chemical being an ohmic electrical conductor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/10251—Elemental semiconductors, i.e. Group IV
    • H01L2924/10253—Silicon [Si]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/156—Material
    • H01L2924/15786—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
    • H01L2924/15787—Ceramics, e.g. crystalline carbides, nitrides or oxides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Die Bonding (AREA)
  • Conductive Materials (AREA)
  • Glass Compositions (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

PURPOSE: To provide a silver/glass paste components to be used for an adhesive agent, especially for adhering a semiconductor device to a substrate, so as to start a sintering process at a comparatively high temperature changing ratio without the used of drying processes. CONSTITUTION: For a silver/glass paste, containing silver flakes, flass flits, organic vehicles and metallic reginates, a surface activator having lyophobic radicals or lyophilic radicals may be contained as well.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、半導体素子、例えば、
珪素ダイ（die ）を適当な基体に付着させるのに有用な
改良された銀・ガラスペーストに関し、更にそのような
ペーストを用いた電子部品の形成方法に関する。BACKGROUND OF THE INVENTION The present invention relates to semiconductor devices such as
It relates to an improved silver-glass paste useful for attaching a silicon die to a suitable substrate, and to a method of forming electronic components using such paste.

【０００２】同様なペーストに関する先行特許には、米
国特許第3,497,774 号；第4,401,767 号；第4,436,785
号；第4,459,166 号；第4,636,254 号；及び第4,761,22
4 号が含まれる。典型的には、これらのペーストは珪素
ダイをセラミック基体に結合するのに用いられる。Prior patents relating to similar pastes include US Pat. Nos. 3,497,774; 4,401,767; 4,436,785.
No. 4,459,166; 4,636,254; and 4,761,22
No. 4 is included. Typically, these pastes are used to bond silicon dies to ceramic substrates.

【０００3 】別の改良された銀・ガラスペースト組成物
は、1991年１月22日に公告された米国特許第4,986,849
号及び1991年２月26日に公告された米国特許第4,996,17
1 号に記載されている。Another improved silver-glass paste composition is disclosed in US Pat. No. 4,986,849 published Jan. 22, 1991.
And U.S. Pat. No. 4,996,17 published February 26, 1991.
It is described in No. 1.

【０００４】当分野で知られているペーストは、典型的
には次の本質的な成分を、下に示す適当な範囲で含んで
いる： 成分 重量％ 銀フレーク 55〜80 ガラスフリット（例えば、鉛硼酸塩ガラス） 10〜25 樹脂又は樹脂形成性成分（例えば、メタクリレート） 0.0〜２ 有機ビヒクル ５〜20 他の添加物、例えば、酸化銀、チキソトロピー化剤、等を含有させてもよい。Pastes known in the art typically contain the following essential ingredients in the appropriate ranges shown below: Ingredient % by Weight Silver Flake 55-80 Glass Frit (eg lead). Borate glass) 10-25 Resin or resin-forming component (e.g. methacrylate) 0.0-2 Organic vehicle 5-20 Other additives such as silver oxide, thixotropic agent, etc. may be contained.

【０００５】代表的なダイ付着方法には、銀フレーク、
ガラスフリット、樹脂及びビヒクルからなるペーストを
セラミック基体中のくぼみに入れ、ダイをそのペースト
上に置き、得られたダイ／基体パッケージをベルトに乗
せ、炉に通し、そこでパッケージを加熱して有機ビヒク
ルを除去し、残留銀及びガラスを焼結し、ダイを基体に
しっかりと結合する。最終的な結合層は完全に気孔（vo
id）を持たないものでなければならず、その結果、その
方法はビヒクルを蒸発させる予備的乾燥工程を必要と
し、次に炉の中で焼成して残留ビヒクルを除去し、ガラ
スを溶融する必要とする。Typical die attachment methods include silver flakes,
A paste consisting of glass frit, resin and vehicle is placed in a depression in a ceramic substrate, a die is placed on the paste, the resulting die / substrate package is placed on a belt and passed through a furnace where the package is heated to drive the organic vehicle. Are removed, the residual silver and glass are sintered, and the die is firmly bonded to the substrate. The final tie layer is completely void (vo
id), as a result, the method requires a preliminary drying step to evaporate the vehicle, then baking in an oven to remove residual vehicle and melting the glass And

【０００６】必要な予備的乾燥工程は極めて長く、例え
ば、ダイの大きさ及び銀フレーク粒子の表面積により、
60〜80℃で約２〜10時間必要とする。更に、変化速度
（ramprate ）、即ちパッケージが乾燥工程から炉中へ
送られる速度は、銀・ガラス混合物の焼結が行われる前
に少なくとも本質的に有機物の燃焼が終わっているよう
に注意深く調節する。ビヒクルの除去及び最適結果を確
実に得るためには、比較的小さい温度変化速度（例え
ば、50℃／分まで）が非常に一般的に用いられている。
焼成段階のためにベルト型炉が通常用いられており、含
まれる温度領域の数によって、炉中の滞留時間は30〜90
分又はそれ以上の範囲になる。The required preliminary drying step is very long, for example due to die size and surface area of silver flake particles,
It takes about 2-10 hours at 60-80 ° C. Furthermore, the ramp rate, ie the rate at which the package is fed from the drying process into the furnace, is carefully adjusted so that at least essentially the combustion of the organics has ended before the sintering of the silver-glass mixture takes place. . Relatively low temperature changes (eg, up to 50 ° C./min) are very commonly used to ensure removal of the vehicle and optimum results.
Belt type furnaces are commonly used for the firing stage, and depending on the number of temperature zones involved, the residence time in the furnace is between 30 and 90.
Minutes or more.

【０００７】大きなダイ、例えば、 400〜500 平方ミル
又はそれ以上のダイを結合する場合、多量の結合剤が必
要であり、その結果かなりの量のビヒクルを蒸発させな
ければならない。ビヒクルの充分な蒸発を行わせるた
め、乾燥工程は特に長く、必要な変化速度は比較的小さ
くする。乾燥時間は小さな銀フレークを用いることによ
り短くすることができ、小さな銀フレークは大きなフレ
ークよりも密に詰まり、そのため乾燥速度を速くするこ
とができる。しかし、小さなフレークを用いた場合、焼
結が早く進み過ぎる傾向があるため、結合部中に亀裂が
形成され易い。従って、慣用的方法を用いて基体に大き
なダイを効果的に取り付けるためには、一般に大きな銀
粒子を使う必要があり、従って、長い乾燥工程及び比較
的小さい温度変化速度を用いる必要がある。When bonding large dies, such as dies of 400 to 500 square mils or more, a large amount of binder is required, which results in the evaporation of a significant amount of vehicle. The drying process is particularly long and the required rate of change is relatively small in order to allow sufficient evaporation of the vehicle. Drying times can be shortened by using small silver flakes, and small silver flakes pack more tightly than large flakes, which allows faster drying rates. However, when small flakes are used, the sintering tends to proceed too quickly, and cracks are likely to form in the joint. Therefore, in order to effectively attach a large die to a substrate using conventional methods, it is generally necessary to use large silver particles, and thus a long drying process and a relatively low temperature change rate.

【０００８】〔本発明の要約〕本発明のペーストは予備
的乾燥工程を省略することができ、大きなダイの場合で
も、ダイ取り付けのための気孔及び亀裂のない結合層を
与えるのに全工程を一層速くすることができる。これら
のペーストは、性能条件を犠牲にすることなく、大きな
温度変化速度で炉に１回通すだけで効果的に用いること
ができる。本発明のペーストの別の利点は今後明らかに
なるであろう。SUMMARY OF THE INVENTION The pastes of the present invention can omit a preliminary drying step, and even in the case of large dies, the entire step is required to provide a porosity and crack-free tie layer for die attachment. Can be even faster. These pastes can be effectively used by passing them once through the furnace at a large rate of temperature change without sacrificing performance conditions. Other advantages of the paste of the present invention will become apparent in the future.

【０００９】広義には、本発明のペーストは、基本的ペ
ースト成分（銀フレーク、ガラスフリット、樹脂及びビ
ヒクル）と共に、一般に金属レジネートとして言及され
ている一種類以上の金属・有機化合物を少量含んでいる
ことを特徴とする。本発明のペーストは、疎液基及び親
液基の両方を有する一種類以上のイオン性又は非イオン
性表面活性剤を含んでいるのが好ましいが、必ずしもそ
うである必要はない。金属レジネートはペースト中の亀
裂を減少させ、且つ（又は）ペーストの接着強度を増大
することが見出されている。米国特許第4,986,849 号で
銀系ペースト中に使用することが記載されている表面活
性剤は、ペーストの安定性を増大し、銀及びガラス粒子
の凝集又は沈降を起こさないか又は最小にし、その結果
ペーストの全性能の改良をもたらすことが見出されてい
る。レジネートは表面活性剤がなくても効果的に用いる
ことができるが、金属レジネートと表面活性剤との併用
は、大きなダイ、例えば、約400 平方ミルを超えるダイ
を結合するのに、予備的乾燥工程を必要とすることな
く、比較的大きな変化速度（例えば、90℃／分）を用い
るて、気孔及び（又は）亀裂を本質的に含まない結合層
を与えるようにペーストを用いることができるようにす
るのに特に効果的であることが見出されている。Broadly speaking, the paste of the present invention comprises, in addition to the basic paste components (silver flakes, glass frits, resins and vehicles), small amounts of one or more metal-organic compounds commonly referred to as metal resinates. It is characterized by being The pastes of the invention preferably, but not necessarily, contain one or more ionic or nonionic surfactants having both lyophobic and lyophilic groups. Metal resinates have been found to reduce cracking in the paste and / or increase the bond strength of the paste. Surfactants described in U.S. Pat.No. 4,986,849 for use in silver-based pastes increase paste stability and prevent or minimize agglomeration or sedimentation of silver and glass particles, resulting in It has been found to provide an improvement in the overall performance of the paste. Although resinates can be used effectively without surfactants, the combination of metal resinates and surfactants does not allow pre-drying to bond large dies, for example, dies greater than about 400 square mils. Allow the paste to be used to provide a tie layer that is essentially free of porosity and / or cracks using a relatively large rate of change (eg, 90 ° C / min) without the need for steps It has been found to be particularly effective at

【００１０】慣用的ペースト中の銀及びガラス成分は、
ファン・デル・ワールス引力のため綿状化する傾向を有
し、銀及びガラス粒子が互いに分離された時、系の自由
エネルギーの増大をもたらす。溶媒又は有機ビヒクルに
対する引力が、あったとしても極めて僅かである疎液基
及びビヒクルに対し強い引力を有する親液基の両方を有
する表面活性剤添加物を用いることにより、綿状化が起
きる傾向は減少し、その結果ペーストの安定性は向上す
る。どのような特定の操作理論によって限定されるもの
ではないが、表面活性剤の疎液基は銀又はガラス粒子の
表面に吸着され、ビヒクルに対する立体障壁を形成する
のに対し、表面活性剤の親液性部分又は「末端」はビヒ
クル又は立体的基中に伸びていると思われる。粒子の綿
状化は、その立体障壁を厚くし、分散粒子を物理的に離
して維持し、粒子相互の衝突効果を減少させることによ
り阻止される。このことはペーストの安定性の増大をも
たらし、その結果上述の如き利点、例えば、乾燥工程を
省略することができること、加熱速度を速くし、短い時
間で珪素ダイと基体との間に気孔及び亀裂のない結合を
得ることができることの利点を与える。The silver and glass components in conventional pastes are
It has a tendency to flocculate due to Van der Waals attraction, resulting in an increase in the free energy of the system when silver and glass particles are separated from each other. Flocculation tends to occur by using a surfactant additive that has both lyophobic groups, if any, that are attractive to solvents or organic vehicles, and lyophilic groups that are strongly attractive to vehicles. Is reduced, resulting in improved paste stability. Without being limited by any particular theory of operation, the lyophobic groups of the surfactant are adsorbed on the surface of the silver or glass particles, forming a steric barrier to the vehicle, whereas the parent of the surfactant. The liquid moiety or "end" is believed to extend into the vehicle or steric group. Fluffing of the particles is prevented by thickening their steric barrier, keeping the dispersed particles physically separated and reducing the effect of collisions between the particles. This leads to an increase in the stability of the paste, so that the advantages mentioned above can be eliminated, for example, the drying step can be omitted, the heating rate can be increased and the pores and cracks between the silicon die and the substrate in a short time. Gives the advantage of being able to obtain a bond free of.

【００１１】慣用的成分と一緒にして表面活性剤だけを
含むペーストは、乾燥工程を用いることなく、大きな温
度変化速度を用いて約 400〜500 平方ミルまでのダイを
よく結合する働きをする。しかし、比較的大きなダイの
結合層は、例えば、屡々約２時間以上の乾燥工程が行わ
れ、続いて小さい温度変化速度を用いない限り、表面活
性剤が添加されていても気孔及び（又は）亀裂を持つ傾
向があるであろう。The paste containing only the surfactant together with the conventional ingredients serves well to bond dies up to about 400-500 square mils with a large temperature change rate without the use of a drying step. However, relatively large die tie layers, for example, often undergo a drying step of about 2 hours or more, followed by pores and / or pores even with the addition of surfactant unless a low rate of temperature change is used. Will tend to have cracks.

【００１２】本発明は、記載の種類の銀系ペーストに金
属レジネートを添加すると或る独特の利点を与えると言
う発見に基づいている。例えば、レジネートを、小さな
銀フレーク、ガラスフリット、有機樹脂又はそのための
成分、ビヒクル及び表面活性剤からなるペースト中に用
いると、乾燥工程を必要とすることなく効果的な結合を
与えることができる。焼成工程中有機物は燃焼除去さ
れ、銀及びガラスの上に薄い金属被覆を残し、それによ
ってペーストの焼結速度が短くなる。比較的大きな変化
速度、例えば、約90℃／分を用いることができる。焼結
速度を小さくすることにより、亀裂の発生を実質的に防
止することができる。本発明によりレジネートを用いる
別の利点は、結合強度を大きくすることができることで
ある。本発明の他の利点も明らかになるであろう。The present invention is based on the discovery that the addition of metal resinates to silver-based pastes of the type described provides certain unique advantages. For example, resinates can be used in pastes consisting of small silver flakes, glass frits, organic resins or components therefor, vehicle and surfactant to provide effective bonding without the need for a drying step. During the firing process, organics are burned away, leaving a thin metallization on the silver and glass, which reduces the sintering rate of the paste. A relatively large rate of change can be used, for example about 90 ° C./min. By reducing the sintering rate, cracking can be substantially prevented. Another advantage of using resinates according to the present invention is that the bond strength can be increased. Other advantages of the invention will also be apparent.

【００１３】本発明で用いられる金属レジネートはよく
知られた種類の化合物を構成する。広義にはそれらは一
つ以上の点に金属を含有する有機分子から構成された有
機金属溶液からなる。レジネートを製造する一つの方法
は、幾つかの有機化合物のいずれかと金属塩と反応させ
ることである。多くの異なった種類の金属レジネート化
合物が本発明の範囲に入り、そのレジネートの重要な特
性は、有機溶液で用いるために高純度金属が与えられて
いると言うことである。The metal resinates used in the present invention constitute a well known class of compounds. Broadly speaking, they consist of an organometallic solution composed of organic molecules containing metal at one or more points. One method of making resinates is by reacting a metal salt with any of several organic compounds. Many different types of metal resinate compounds fall within the scope of this invention, and an important property of the resinate is that it provides a high purity metal for use in organic solutions.

【００１４】本発明によれば、好ましくは約 0.8〜1.5
m2／g の比表面積を有する銀フレークが用いられ、一層
大きなフレークを用いた場合よりも一層よい充填を与
え、従って、気孔を生ずることなくビヒクルの蒸発を速
くすることができる。従来の処理で大きさの小さなフレ
ークを用いると、焼成で焼結が速く起きると結合層に亀
裂を生ずる傾向があるのに対し、金属レジネートを添加
すると、小さな大きさの銀フレークを用いても、亀裂を
起こさず且つ（又は）接着を向上させることが見出され
ている。According to the present invention, preferably about 0.8-1.5.
Silver flakes with a specific surface area of m 2 / g are used and give better packing than with larger flakes, thus allowing faster vehicle evaporation without the formation of porosity. Whereas conventional treatments with smaller flake sizes tend to crack the tie layer when sintering quickly occurs on firing, the addition of metal resinate allows the use of smaller flake sizes. It has been found that it does not crack and / or improves adhesion.

【００１５】本発明のレジネート含有ペーストは種々の
大きさのダイを結合するのに用いることができる。しか
し、そのペーストは、もしレジネートが用いられていな
いと通常は処理過程で乾燥工程を必要とするような大き
なダイを結合するのに特に有用である。The resinate-containing paste of the present invention can be used to bond dies of various sizes. However, the paste is particularly useful for bonding large dies, which usually require a drying step in the process if the resinate is not used.

【００１６】〔本発明の詳細な記述〕用いられる金属レ
ジネートは、焼結温度で銀中に溶解しないものが好まし
い。このことが最もよい接着結果を与えるように見え
る。そのようなレジネートには、コバルト、ロジウム、
及びイリジウムのレジネートが含まれる。しかし、バリ
ウム、マグネシウム、カルシウム、及び鉛のレジネート
の如き他の金属レジネートも用いることができる。明ら
かにレジネートは銀フレークを被覆することによってそ
の機能を果たす。従って、レジネートの使用量は広く変
えることができるが、最もよい結果を得るためには全て
の銀フレークを本質的に被覆するのに充分な量で用いる
べきである。一般的に言って、これは、ペーストの全重
量に基づき約0.01〜５重量％、好ましくは 0.1重量％の
金属レジネートの量になるであろう。有用なレジネート
は市販されている。例えば、エンゲルハード・ミネラル
ズ・アンド・ケミカルズ社（Engelhard Minerals & Che
micals Corporation）のエンゲルハード・インダストリ
ーズ・ディビジョン(Engelhard Industries Division）
の「純粋金属レジネート」（Pure Metal Resinates）と
題するカタログ、及びホッパー・セラミック・インダス
トリー（Hopper, Ceramic Industry）による「セラミッ
クスへの貴金属適用方法」（How to Apply Noble Metal
s to Ceramics）（1963年６月）と題する文書を参照さ
れたい。一般に、適当な金属レジネートは、約 300℃よ
り高い温度で安定なものである。Detailed Description of the Invention The metal resinate used is preferably one that does not dissolve in silver at the sintering temperature. This seems to give the best adhesion results. Such resinates include cobalt, rhodium,
And iridium resinate. However, other metal resinates such as barium, magnesium, calcium, and lead resinates can also be used. Apparently the resinate fulfills its function by coating the silver flakes. Therefore, the amount of resinate used can vary widely but should be used in an amount sufficient to essentially cover all silver flakes for best results. Generally speaking, this will amount to about 0.01 to 5% by weight, preferably 0.1% by weight metal resinate, based on the total weight of the paste. Useful resinates are commercially available. For example, Engelhard Minerals & Che
micals Corporation) Engelhard Industries Division
"Pure Metal Resinates" catalog and "How to Apply Noble Metal to Ceramics" by Hopper, Ceramic Industry
s to Ceramics) (June 1963). In general, suitable metal resinates are stable at temperatures above about 300 ° C.

【００１７】金属レジネートはペーストを配合するどの
ような都合のよい段階で添加してもよい。一つの好まし
い態様として、銀フレーク、金属レジネート、及びビヒ
クルを、もし表面活性剤を用いるならば、それと一緒に
混合し、然る後、ガラスを添加する。しかし、別法とし
て、ペースト成分の全てを一度に一緒に混合し、均一な
配合物が得られるまで混合してもよい。通常均質な組成
物を与えるのに、２〜６時間の低剪断混合が適切であ
る。The metal resinate may be added at any convenient stage in formulating the paste. In one preferred embodiment, the silver flakes, metal resinate, and vehicle are mixed with the surfactant, if used, before the glass is added. Alternatively, however, all of the paste components may be mixed together at once and mixed until a uniform formulation is obtained. Low shear mixing for 2 to 6 hours is usually suitable to give a homogeneous composition.

【００１８】表面活性剤を用いる場合、それは疎液基及
び親液基の両方を含むのがよく、約300℃より高い温
度、即ち、銀・ガラス混合物の焼結が始まる温度に近い
か又はそれより高い温度で安定であるべきである。疎液
基は長鎖炭化水素基であるのに対し、親液基はイオン性
又は高度に極性の基であるのが有利である。疎液基の例
を次に挙げる：If a surface-active agent is used, it should contain both lyophobic and lyophilic groups, a temperature above about 300 ° C., ie close to or at which the sintering of the silver-glass mixture begins. It should be stable at higher temperatures. The lyophobic group is a long-chain hydrocarbon group, while the lyophilic group is advantageously an ionic or highly polar group. Examples of lyophobic groups are:

【００１９】Ｃ8 〜Ｃ20直鎖又は分岐鎖アルキル；Ｃ8
〜Ｃ20アルキルで置換されたフェニル基；３以上の炭素
を有するアルキルで置換されたナフチル基；ロジン誘導
体；高分子量酸化プロピレン重合体（ポリオキシプロピ
レングリコール誘導体）；等。C 8 -C 20 straight or branched chain alkyl; C 8
A phenyl group substituted with C 20 alkyl; a naphthyl group substituted with an alkyl having 3 or more carbons; a rosin derivative; a high molecular weight propylene oxide polymer (polyoxypropylene glycol derivative);

【００２０】親液性成分として、式ＲＣＯＯＣＨ2 ＣＨ
ＯＣＣＨ2 ＯＨ〔式中、Ｒは長鎖アルキル（例えば、Ｃ
12以上）〕の長鎖脂肪酸及び（又は）式Ｒ−Ｃ6 Ｈ
4 （ＯＣ 2 Ｈ4 ）x ＯＨ（式中、Ｒは８〜20個の炭素原
子のアルキルであり、x は整数、例えば、１〜70の整数
である）のポリオキシエチレン化アルキルフェノールの
モノグリセリド、それらの硫酸化誘導体、及びそのよう
な誘導体のアルカリ金属塩の如き非イオン性材料を挙げ
ることができる。As the lyophilic component, the formula RCOOCH2CH
OCCH2OH [wherein R is a long-chain alkyl (for example, C
12Above)]] long-chain fatty acid and / or formula RC6H
Four(OC 2HFour) X OH (where R is 8 to 20 carbon atoms)
Is a child alkyl, and x is an integer, for example, an integer of 1 to 70.
Of polyoxyethylenated alkylphenol
Monoglycerides, their sulfated derivatives, and the like
Examples of nonionic materials such as alkali metal salts of various derivatives
You can

【００２１】ここで用いるのに適した疎液及び親液基の
両方を含む表面活性剤の特別な例として、次のものを挙
げることができる：トリトン（Triton）（エトキシル化
及び硫酸化されたオクチルフェノールのナトリウム
塩）、プルロニック（Pluronic）（酸化エチレン酸化プ
ロピレンブロック共重合体）、テトロニック（Tetroni
c）（脂肪アミンエトキシレート）、ポスト（Post）−
４（水素化ひまし油）、ティナゲル（Tinagel ）（脂肪
アミンエトキシレート）、及びレシチン（β−Ｎ−アル
キルアミノプロピオン酸）。Specific examples of surfactants containing both lyophobic and lyophilic groups suitable for use herein include: Triton (ethoxylated and sulfated Octylphenol sodium salt), Pluronic (ethylene oxide propylene oxide block copolymer), Tetroni (Tetroni
c) (fatty amine ethoxylate), Post-
4 (hydrogenated castor oil), Tinagel (fatty amine ethoxylates), and lecithin (β-N-alkylaminopropionic acid).

【００２２】表面活性剤の使用量は比較的広く変化させ
ることができるが、少なくともある程度まで用いられる
表面活性剤に依存するであろう。しかし、通常表面活性
剤はペースト、即ち、銀、ガラス、樹脂、ビヒクル。表
面活性剤及び金属レジネートの全重量に基づき、0.05〜
２重量％を占めるであろう。表面活性剤はペースト配合
のどのような便利な段階で添加してもよい。The amount of surfactant used can vary relatively widely, but will depend, at least to some extent, on the surfactant used. However, usually the surface active agent is a paste: silver, glass, resin, vehicle. Based on the total weight of surfactant and metal resinate, 0.05-
It will account for 2% by weight. The surfactant may be added at any convenient stage in the paste formulation.

【００２３】金属レジネートの添加、及び上述した如く
任意ではあるが使用した方が好ましい表面活性剤の添加
とは別に、ペーストは慣用的成分を含んでいる。本発明
のペーストで用いられる銀フレークは、当分野で慣用的
に用いられている種類のものでよい。そのようなフレー
クは 0.4〜1.5 m2／g の比表面積、及び 2.5〜4.0g／cc
のタップ（tap ）密度を有するのが典型的である。本発
明の目的にとって、銀フレークは本質的に均質な大きさ
であるのが好ましいが、粉砕されたものでは種々のもの
がフレークになっているであろう。フレークの使用量は
変化させることができるが、通常ペーストの全重量に基
づき、55〜75％の範囲に入るであろう。Apart from the addition of the metal resinate and, as mentioned above, the optional but preferably used surfactant, the paste contains conventional constituents. The silver flakes used in the pastes of the present invention may be of the type conventionally used in the art. Such flakes have a specific surface area of 0.4-1.5 m 2 / g and 2.5-4.0 g / cc
It typically has a tap density of. For the purposes of the present invention, it is preferred that the silver flakes are essentially homogeneous in size, although the ground ones will be flakes of a variety. The amount of flakes used can vary but will usually be in the range 55-75% based on the total weight of the paste.

【００２４】ガラス成分は、シリカ及びナトリウムを含
まない鉛硼酸塩ガラスフリットでもよい。通常このガラ
スは、 325℃〜425 ℃の範囲の軟化点、約15 ppm／℃以
下の熱膨張係数、少なくとも約 0.3m2／g の比表面積、
及び約４ g／ccまでのタップ密度を有する鉛硼酸塩フリ
ットからなるであろう。通常ガラスはペーストの重量の
約10〜25％を占めるであろう。The glass component may be silica and sodium free lead borate glass frit. Generally, this glass has a softening point in the range of 325 ° C to 425 ° C, a coefficient of thermal expansion of about 15 ppm / ° C or less, a specific surface area of at least about 0.3 m 2 / g,
And a lead borate frit having a tap density of up to about 4 g / cc. Usually glass will make up about 10-25% of the weight of the paste.

【００２５】別法として、米国特許第4,996,171 号に記
載されているような鉛燐酸塩バナジウム酸塩ガラスを用
いてもよい。Alternatively, lead phosphate vanadate glasses such as those described in US Pat. No. 4,996,171 may be used.

【００２６】本発明の目的のために種々の異なった有機
樹脂成分を用いることができる。これにはメチル、エチ
ル、又はイソブチルメタクリレートの如き低級アルキル
メタクリレートが含まれ、後者のものが好ましい。この
成分は通常ペーストの約 0.5〜2.0 重量％を占める。A variety of different organic resin components can be used for the purposes of the present invention. This includes lower alkyl methacrylates such as methyl, ethyl, or isobutyl methacrylate, the latter being preferred. This component usually comprises about 0.5 to 2.0% by weight of the paste.

【００２７】有機ビヒクルの組成は広く変えることがで
きる。しかし、ビヒクルは 120〜200 ℃の沸点範囲を持
つものであるべきである。これによって乾燥を必要とし
ない一回の通過でよいペーストが可能になる。特に有効
な溶媒は、アルコール、特に２−オクタノール、好まし
くは少量（例えば、溶媒全量の１〜20重量％）の、ベン
ジルアルコール及び４−ヒドロキシ−３−メトキシベン
ズアルデヒドの如き添加物と混合したそれらからなる。
通常ペーストは重量基準で10〜20％のビヒクルを含むで
あろう。The composition of the organic vehicle can vary widely. However, the vehicle should have a boiling range of 120-200 ° C. This allows for a single pass good paste that does not require drying. Particularly effective solvents are alcohols, especially 2-octanol, preferably those which have been mixed in small amounts (eg 1 to 20% by weight of the total solvent) with additives such as benzyl alcohol and 4-hydroxy-3-methoxybenzaldehyde. Become.
Usually the paste will contain 10-20% vehicle by weight.

【００２８】本発明のペーストには、本発明から離れる
ことなく、他の添加物、例えば酸化銀、チキソトロピー
化剤等が含まれていてもよい。The paste of the present invention may contain other additives such as silver oxide, a thixotropic agent, etc. without departing from the present invention.

【００２９】本発明の代表的な組成物の製造及び使用を
例示する次の実施例により本発明を例示するが、それに
よって限定されるものではない。The invention is illustrated, but not limited, by the following examples which illustrate the preparation and use of representative compositions of the invention.

【００３０】 例Ａ 記載した成分を、重量％で示した量で一緒に混合する
ことにより次の組成物を 製造した： 銀フレーク 約 69％ 鉛硼酸塩ガラス 約 17％ ポリイソブチルメタクリレート 約 １％ エチレングリコール二酢酸 約 5.5％ ２，２，４トリメチルペンタンジオール− １，３モノイソブチレート（テキサノール） 約 ７％ トリトンＸ100 約 0.5％Example A The following composition was prepared by mixing together the components described in the amounts indicated in weight%: silver flakes about 69% lead borate glass about 17% polyisobutyl methacrylate about 1% ethylene. Glycol diacetic acid About 5.5% 2,2,4 Trimethylpentanediol-1,3 monoisobutyrate (Texanol) About 7% Triton X100 About 0.5%

【００３１】Ａとするこの組成物は金属レジネートを含
まず、下に記載するように比較の目的で用いられた。This composition, designated A, contained no metal resinate and was used for comparative purposes as described below.

【００３２】例Ｂ 例Ａを繰り返した。但し市販のＲｈレジネート 0.5％を
組成物に含有させ、組成物Ｂを与えた。Example B Example A was repeated. However, 0.5% of commercially available Rh resinate was included in the composition to give composition B.

【００３３】例Ｃ 例Ｂを繰り返した。但しＲｈレジネートを 0.5重量％の
Ｃｏレジネートで置き換えた。Example C Example B was repeated. However, the Rh resinate was replaced with 0.5 wt% Co resinate.

【００３４】例Ｄ 例Ｂを繰り返した。但し 0.5重量％のＰｄレジネート
を、Ｒｈレジネートの代わりに添加物として用いた。Example D Example B was repeated. However, 0.5 wt% Pd resinate was used as an additive instead of Rh resinate.

【００３５】例Ｅ 例Ｂを繰り返した。但しこの場合には金属レジネートは
0.5重量％のＢａレジネートであった。Example E Example B was repeated. However, in this case, the metal resinate
It was 0.5 wt% Ba resinate.

【００３６】例Ｆ 例Ｂを繰り返した。但しＲｈレジネートの代わりに 0.5
重量％のＰｂレジネートを用いた。Example F Example B was repeated. However, instead of Rh resinate, 0.5
Weight percent Pb resinate was used.

【００３７】例Ａ〜Ｆの組成物を用いて慣用的珪素ダイ
を裸のセラミック基体へ結合した。用いた方法は、ペー
ストをセラミック基体上のダイ空腔へ適用し、そのペー
ストの上にダイを乗せ、得られたパッケージを慣用的ベ
ルト炉に通してダイを基体へ結合した。変化速度は約90
℃／分であった。予備的な乾燥工程は用いなかった。炉
は最高 430℃の温度で操作した。焼成過程は20分で完了
した。冷却後、ダイと基体との間の結合を気孔％、亀裂
％、及び接着性（１in当たりのlb）について調べた。結
果を下の表に示す：A conventional silicon die was bonded to a bare ceramic substrate using the compositions of Examples AF. The method used was to apply the paste to a die cavity on a ceramic substrate, place the die on top of the paste, and pass the resulting package through a conventional belt oven to bond the die to the substrate. The rate of change is about 90
° C / min. No preliminary drying step was used. The furnace was operated at temperatures up to 430 ° C. The firing process was completed in 20 minutes. After cooling, the bond between the die and the substrate was examined for% porosity,% cracking, and adhesion (lb / in). The results are shown in the table below:

【００３８】[0038]

【表１】 表１ 組成物 添加物％ 気孔％ 亀裂％ 接着性（lb／in） Ａ 0 2 100 17 Ｂ 0.5 （Ｒｈ） 0 0 49 Ｃ 0.5 （Ｃｏ） 0 5 31 Ｄ 0.5 （Ｐｄ） 2 75 3.3 Ｅ 0.5 （Ｂａ） 0 100 74 Ｆ 0.5 （Ｐｂ） 0 100 34Table 1 Composition additive% Porosity% Crack% Adhesion (lb / in) A 0 2 100 17 B 0.5 (Rh) 0 0 49 C 0.5 (Co) 0 5 31 D 0.5 (Pd) 2 75 3.3 E 0.5 (Ba) 0 100 74 F 0.5 (Pb) 0 100 34

【００３９】前記結果は、各例で金属レジネートを用い
ると（例Ｂ〜Ｆ）、気孔或は亀裂がかなり少なくなり且
つ（又は）一層大きな接着性を持つ結合を与えているこ
とを示している。The above results show that the use of metal resinates in each case (Examples BF) gives a bond with significantly less porosity or cracking and / or greater adhesion. .

【００４０】Ｒｈ及びＣｏレジネートは亀裂防止性及び
接着性の両方を改良する機能を持つことに注意すべきで
ある。これらのレジネートは銀に溶解しない。Ｐｄレジ
ネートは銀に溶解し、従って、200 ℃以上の焼結温度で
固溶体になる。これは明らかに指示試験条件でＰｄレジ
ネートを用いたことから生じた接着性の低下の原因にな
っている。It should be noted that Rh and Co resinates have the function of improving both crack resistance and adhesion. These resinates do not dissolve in silver. Pd resinate dissolves in silver and therefore becomes a solid solution at sintering temperatures above 200 ° C. This clearly accounts for the poor adhesion resulting from the use of Pd resinate in the indicated test conditions.

【００４１】上記例は鉛硼酸塩ガラスを基にしたペース
トを用いた本発明を例示しているが、本発明は、前に記
載した他の種類のガラスと共に用いることもできる。こ
れに関し、米国特許第4,996,171 号に記載された鉛燐酸
塩バナジウム酸塩ガラスと共に、米国特許第4,986,849
号に記載されたような金属レジネート及び任意に表面活
性剤を用いるのが特に有利であることが判明している。
或る状況下では、約 420〜430 ℃の焼成温度を通常必要
とする鉛硼酸塩ガラスを基にしたペーストは、或る種類
のパッケージに対しては、例えばはんだ密封パッケージ
で望ましくないニッケル拡散の如き処理問題を起こすこ
とがある。他の或る種類のパッケージも、 350〜380 ℃
程度の低い焼成温度を必要とすることがある。そのよう
な場合、例えば、 350℃位の低い温度で焼成することが
できる鉛燐酸塩バナジウム酸塩ガラスを用いるのが有利
であることが判明している。本発明による典型的なその
ようなペーストは、ペーストの全重量を基準にして次の
ものからなっているであろう：Although the above example illustrates the present invention using a paste based on lead borate glass, the present invention can also be used with the other types of glass described above. In this regard, U.S. Pat. No. 4,986,849, along with lead phosphate vanadate glasses described in U.S. Pat.
It has been found to be particularly advantageous to use a metal resinate as described in US Pat.
Under some circumstances, pastes based on lead borate glass, which normally require firing temperatures of about 420-430 ° C., lead to undesired nickel diffusion for some types of packages, for example solder-sealed packages. Such a processing problem may occur. Other types of packages are also 350-380 ° C
A low firing temperature may be required. In such cases, it has proved advantageous to use lead phosphate vanadate glasses which can be fired at temperatures as low as, for example, 350 ° C. A typical such paste according to the invention will consist of the following, based on the total weight of the paste:

【００４２】（１） 0.4〜1.5 m2／g の比表面積及び
2.5〜４ g／ccの範囲のタップ密度を有する前に記述し
たような銀フレーク約55〜80重量％、(1) 0.4 to 1.5 m 2 / g specific surface area and
About 55-80% by weight of silver flakes as previously described having a tap density in the range of 2.5-4 g / cc,

【００４３】（２） 250〜350 ℃の軟化点、少なくと
も 0.3m2／g の比表面積、約 2.5 g／ccのタップ密度を
有する鉛燐酸塩バナジウム酸塩ガラス約８〜20重量％、(2) About 8 to 20% by weight of lead phosphate vanadate glass having a softening point of 250 to 350 ° C., a specific surface area of at least 0.3 m 2 / g, and a tap density of about 2.5 g / cc,

【００４４】（３） 疎水性基及び親水性基の両方を有
するイオン性又は非イオン性表面活性剤である米国特許
出願Ｓerial Ｎo.07／248,120 に記載されているような
表面活性剤、例えば、トリトンＸ、プルロニック、テト
ロニック等約0.05〜２重量％、(3) Surfactants such as those described in US patent application Serial No. 07 / 248,120 which are ionic or nonionic surfactants having both hydrophobic and hydrophilic groups, eg Triton X, Pluronic, Tetronic, etc. about 0.05-2% by weight,

【００４５】（４） 金属レジネート、例えばバリウ
ム、マグネシウム、カルシウムのレジネート又は他のガ
ラス湿潤剤約0.05〜２重量％、(4) Metal resinates, such as barium, magnesium, calcium resinates or other glass wetting agents, about 0.05 to 2% by weight;

【００４６】（５） 好ましくは乾燥工程のない一回通
過法を可能にする、 120〜220 ℃の範囲の沸点を持つ溶
媒又は液体ビヒクル10〜20重量％。(5) 10 to 20% by weight of solvent or liquid vehicle having a boiling point in the range of 120 to 220 ° C., which allows a single pass process, preferably without a drying step.

【００４７】そのような組成物の例として、重量％によ
る次のものを挙げることができる： 銀フレーク 約76 ％ 鉛燐酸塩バナジウム酸塩ガラス 10 ％ イソブチルメタクリレート 0.5 ％ ベンジルアルコール 7.5 ％ エチレングリコールジアセテート 5.0 ％ トリトンＸ100 0.5 ％ バリウムレジネート 0.5 ％ 100 ％As an example of such a composition the following may be mentioned, by weight%: silver flakes about 76% lead phosphate vanadate glass 10% isobutyl methacrylate 0.5% benzyl alcohol 7.5% ethylene glycol diacetate. 5.0% Triton X100 0.5% Barium Resinate 0.5% 100%

【００４８】300 ミルダイを結合するのにこのペースト
を用い、40℃／分の変化速度及び最高 360℃の温度を５
〜８分間用いることにより、平均接着性値42を有する無
気孔無亀裂の結合を与えたのに対し、同様なペーストを
トリトン及びレジネートを用いなかった場合（ａ）及び
トリトンを用いたがレジネートは用いなかった場合
（ｂ）に対し夫々22及び34の平均接着性値が得られた。
どの場合でも無気孔無亀裂の結合が得られた。This paste was used to bond a 300 mil die with a rate of change of 40 ° C./min and a temperature of up to 360 ° C.
~ 8 minutes gave a pore-free and crack-free bond with an average adhesion value of 42, whereas a similar paste was used without triton and resinate (a) and with triton but resinate. Average adhesion values of 22 and 34 respectively were obtained for (b) when not used.
Pore-free and crack-free bonding was obtained in all cases.

【００４９】ここで意図されているペーストの更に別な
変更は、特に望ましい形の有機ビヒクルを与えることで
ある。通常、銀充填ガラスペーストの有機ビヒクルは、
重合体樹脂と溶媒との液体溶液からなり、その銀とガラ
スとの混合物は希望のペースト状態を与える。ダイ付着
の一般的方法は、適当な量のペーストを基体に適用し、
次にそのペーストの上にダイを乗せることを含んでい
る。次に複合体を炉に通して有機物を燃焼除去し、ダイ
を基体に強く結合する。銀・ガラスペーストを適用する
方法は比較的ゆっくりである。A further modification of the pastes contemplated herein is to provide the organic vehicle in a particularly desirable form. Usually, the organic vehicle of silver-filled glass paste is
It consists of a liquid solution of a polymer resin and a solvent, the mixture of silver and glass of which gives the desired paste state. The general method of die attachment is to apply an appropriate amount of paste to the substrate,
Then include placing a die on top of the paste. The composite is then passed through a furnace to burn off the organics and firmly bond the die to the substrate. The method of applying the silver-glass paste is relatively slow.

【００５０】ここで意図されている更に別な変更は、室
温（20〜25℃）で固化し、例えば、70℃以上の融点を有
するビヒクルを与えることである。銀及びガラスをビヒ
クル中にその融点より高い温度で混合する。これによっ
て室温で固体であるが、70℃より高い温度で液体になる
混合物が与えられる。Yet another modification contemplated herein is to solidify at room temperature (20-25 ° C) to provide a vehicle having a melting point of, for example, 70 ° C or above. Silver and glass are mixed in the vehicle at a temperature above its melting point. This gives a mixture that is solid at room temperature but liquid at temperatures above 70 ° C.

【００５１】この型の材料を珪素ウェーハの裏側又は基
体空腔上に70℃より高い温度で液体として適用すること
ができる。次にペーストを固化し、希望の結合になるま
で適所に維持する。次にウェーハ又はダイをその基体と
一緒にし、加熱して希望の結合を行わせる。このように
してペーストをウェーハ又はダイ製造の一部として、又
は基体製造の一部として予め適用することができる。こ
れによってダイの取付け自体を一層速く且つ一層正確に
することができる。結合過程中、固体有機ビヒクルは、
慣用的ビヒクルが用いられた場合と同様に、 250℃で完
全に燃焼除去され、ダイと基体とを結合する無機銀ガラ
スを残す。This type of material can be applied as a liquid at a temperature above 70 ° C. on the back side of a silicon wafer or on a substrate cavity. The paste is then solidified and held in place until the desired bond is achieved. The wafer or die is then brought together with its substrate and heated to effect the desired bond. In this way the paste can be pre-applied as part of wafer or die manufacture or as part of substrate manufacture. This allows the die attachment itself to be faster and more accurate. During the binding process, the solid organic vehicle
It is burnt out completely at 250 ° C., leaving the inorganic silver glass bonding the die and substrate, as if a conventional vehicle was used.

【００５２】この更に別の変更に従う代表的な固体ビヒ
クルは、重量％で示した次のものである。 ステアリルアルコール 約65％ バラフィンワックス 20％ エルバサイト（Elvacite）2042 10％ トリトンＸ 100 5％A typical solid vehicle in accordance with this further modification is the following in weight percent: Stearyl alcohol About 65% Balafin wax 20% Elvacite 2042 10% Triton X 100 5%

【００５３】このビヒクルは室温で固体であるが、約70
℃で溶融し、効果的な結合を与える。そのようなビヒク
ルを含む典型的なペーストは、例えば、64％の銀フレー
ク、16％のガラス、20％のビヒクル（％は重量による）
からなっていてもよい。本発明のこの態様は上記特定の
ビヒクル及びペースト組成物に限定されるものではな
い。特に、室温で固体であり、例えば、65〜80℃で溶融
する他のビヒクルも本発明の目的のために用いてもよ
い。本発明は、特許請求の範囲で規定されるものであ
る。This vehicle is a solid at room temperature,
Melts at ° C to give an effective bond. A typical paste containing such a vehicle is, for example, 64% silver flakes, 16% glass, 20% vehicle (% by weight).
May consist of This aspect of the invention is not limited to the particular vehicle and paste compositions described above. In particular, other vehicles that are solid at room temperature and melt at, for example, 65-80 ° C may also be used for the purposes of the present invention. The invention is defined by the claims.

Claims (15)

【特許請求の範囲】[Claims] 【請求項１】 銀フレーク、ガラスフリット、有機ビヒ
クル、及び金属レジネートからなる銀・ガラスペース
ト。1. A silver / glass paste comprising silver flakes, glass frits, an organic vehicle, and a metal resinate. 【請求項２】 表面活性剤を更に含む請求項１に記載の
ペースト。2. The paste according to claim 1, further comprising a surfactant. 【請求項３】 銀フレークの比表面積が 0.4〜1.5 m2／
g であり、タップ密度が 2.5〜4.0g／ccである請求項１
に記載のペースト。3. The specific surface area of silver flakes is 0.4 to 1.5 m 2 /
g and the tap density is 2.5 to 4.0 g / cc.
Paste described in. 【請求項４】 金属レジネートの量がペーストの約0.01
〜５重量％である請求項２に記載のペースト。4. The amount of metal resinate is about 0.01 of the paste.
The paste according to claim 2, which is -5% by weight. 【請求項５】 表面活性剤の量がペーストの0.05〜２重
量％である請求４項に記載のペースト。5. The paste according to claim 4, wherein the amount of surfactant is 0.05 to 2% by weight of the paste. 【請求項６】 55〜80％の銀フレーク、10〜25％の鉛硼
酸塩ガラス、及び 0.0〜２％の樹脂を含む請求項５に記
載のペースト。6. The paste according to claim 5, comprising 55-80% silver flakes, 10-25% lead borate glass, and 0.0-2% resin. 【請求項７】 金属レジネートがＰｂ、Ｐｄ、Ｍｇ、Ｃ
ａ、Ｂａ、Ｒｈ、又はＣｏのレジネートからなる請求項
１に記載のペースト。7. The metal resinate is Pb, Pd, Mg, C.
The paste according to claim 1, comprising a resinate of a, Ba, Rh, or Co. 【請求項８】 ガラスが、鉛燐酸塩バナジウム酸塩ガラ
スである請求項１に記載のペースト。8. The paste according to claim 1, wherein the glass is lead phosphate vanadate glass. 【請求項９】 請求項１に記載の銀・ガラスペーストを
基体に適用し、該ペースト上に珪素ダイを置き、次に前
記銀とガラスを焼結して前記ダイを基体に結合する諸工
程からなる基体に珪素ダイを結合する方法。9. The steps of applying the silver-glass paste of claim 1 to a substrate, placing a silicon die on the paste, and then sintering the silver and glass to bond the die to the substrate. A method of bonding a silicon die to a substrate made of. 【請求項10】 ダイが少なくとも 400平方ミルの表面積
を有する請求項９に記載の方法。10. The method of claim 9, wherein the die has a surface area of at least 400 square mils. 【請求項11】 金属レジネートが、Ｐｂ、Ｐｄ、Ｂａ、
Ｒｈ、又はＣｏレジネートからなる請求項９に記載の方
法。11. The metal resinate is Pb, Pd, Ba,
The method according to claim 9, which comprises Rh or Co resinate. 【請求項12】 金属レジネートをペーストへ添加する工
程を含む、慣用的銀・ガラスペーストの結合強度を増大
する方法。12. A method of increasing the bond strength of a conventional silver-glass paste comprising the step of adding a metal resinate to the paste. 【請求項13】 基体と、結合剤により前記基体に付着さ
れた半導体素子とからなり、然も、前記結合剤が請求項
１に記載の銀充填ガラスペーストである製造物品。13. An article of manufacture comprising a substrate and a semiconductor device attached to the substrate with a binder, wherein the binder is the silver filled glass paste of claim 1. 【請求項14】 半導体素子が少なくとも400 平方ミルの
表面積を有する請求項13に記載の製造物品。14. The article of manufacture of claim 13, wherein the semiconductor device has a surface area of at least 400 square mils. 【請求項15】 ビヒクルが、室温で固体であるが約70℃
より高い温度で溶融するものである請求項１に記載のペ
ースト。15. The vehicle is solid at room temperature but at about 70 ° C.
The paste according to claim 1, which melts at a higher temperature.
JP3027411A 1990-02-21 1991-02-21 Silver-glass paste Pending JPH056909A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US482489 1990-02-21
US07/482,489 US5075262A (en) 1990-02-21 1990-02-21 Silver-glass pastes

Publications (1)

Publication Number Publication Date
JPH056909A true JPH056909A (en) 1993-01-14

Family

ID=23916294

Family Applications (1)

Application Number Title Priority Date Filing Date
JP3027411A Pending JPH056909A (en) 1990-02-21 1991-02-21 Silver-glass paste

Country Status (6)

Country Link
US (1) US5075262A (en)
EP (1) EP0443842A1 (en)
JP (1) JPH056909A (en)
KR (1) KR910021458A (en)
CN (1) CN1055164A (en)
TW (1) TW204333B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008192455A (en) * 2007-02-05 2008-08-21 Narumi China Corp Glass top plate for heating cooker
JP2012513683A (en) * 2008-12-23 2012-06-14 ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング Electrical or electronic composite component and method for manufacturing electrical or electronic composite component
JPWO2011158753A1 (en) * 2010-06-17 2013-08-19 日立化成株式会社 Resin paste composition

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5183784A (en) * 1990-02-21 1993-02-02 Johnson Matthey Inc. Silver-glass pastes
US5378408A (en) * 1993-07-29 1995-01-03 E. I. Du Pont De Nemours And Company Lead-free thick film paste composition
US5882722A (en) * 1995-07-12 1999-03-16 Partnerships Limited, Inc. Electrical conductors formed from mixtures of metal powders and metallo-organic decompositions compounds
US6338809B1 (en) * 1997-02-24 2002-01-15 Superior Micropowders Llc Aerosol method and apparatus, particulate products, and electronic devices made therefrom
CA2280865C (en) 1997-02-24 2008-08-12 Superior Micropowders Llc Aerosol method and apparatus, particulate products, and electronic devices made therefrom
US20030148024A1 (en) * 2001-10-05 2003-08-07 Kodas Toivo T. Low viscosity precursor compositons and methods for the depositon of conductive electronic features
US6951666B2 (en) * 2001-10-05 2005-10-04 Cabot Corporation Precursor compositions for the deposition of electrically conductive features
US7524528B2 (en) 2001-10-05 2009-04-28 Cabot Corporation Precursor compositions and methods for the deposition of passive electrical components on a substrate
US20030108664A1 (en) * 2001-10-05 2003-06-12 Kodas Toivo T. Methods and compositions for the formation of recessed electrical features on a substrate
US7629017B2 (en) 2001-10-05 2009-12-08 Cabot Corporation Methods for the deposition of conductive electronic features
US7732002B2 (en) 2001-10-19 2010-06-08 Cabot Corporation Method for the fabrication of conductive electronic features
US7553512B2 (en) 2001-11-02 2009-06-30 Cabot Corporation Method for fabricating an inorganic resistor
US6878184B1 (en) 2002-08-09 2005-04-12 Kovio, Inc. Nanoparticle synthesis and the formation of inks therefrom
US7078276B1 (en) 2003-01-08 2006-07-18 Kovio, Inc. Nanoparticles and method for making the same
CN1296301C (en) * 2004-12-30 2007-01-24 贵州振华亚太高新电子材料有限公司 Lead-free electroplated silver slurry for outer electrode of multilayer chip element
WO2006076612A2 (en) 2005-01-14 2006-07-20 Cabot Corporation A process for manufacturing application specific printable circuits (aspc’s) and other custom electronic devices
US8334464B2 (en) 2005-01-14 2012-12-18 Cabot Corporation Optimized multi-layer printing of electronics and displays
WO2006076610A2 (en) * 2005-01-14 2006-07-20 Cabot Corporation Controlling ink migration during the formation of printable electronic features
US8383014B2 (en) 2010-06-15 2013-02-26 Cabot Corporation Metal nanoparticle compositions
WO2006076609A2 (en) 2005-01-14 2006-07-20 Cabot Corporation Printable electronic features on non-uniform substrate and processes for making same
WO2006076608A2 (en) 2005-01-14 2006-07-20 Cabot Corporation A system and process for manufacturing custom electronics by combining traditional electronics with printable electronics
US7824466B2 (en) 2005-01-14 2010-11-02 Cabot Corporation Production of metal nanoparticles
PL218232B1 (en) 2010-09-16 2014-10-31 Inst Technologii Materiałów Elektronicznych Nanosilver conductive paste, especially for high current and high temperature applications
US10700234B2 (en) 2017-08-17 2020-06-30 California Institute Of Technology Fabrication processes for effectively transparent contacts
US11227964B2 (en) 2017-08-25 2022-01-18 California Institute Of Technology Luminescent solar concentrators and related methods of manufacturing
US11362229B2 (en) 2018-04-04 2022-06-14 California Institute Of Technology Epitaxy-free nanowire cell process for the manufacture of photovoltaics
WO2020041522A1 (en) 2018-08-21 2020-02-27 California Institute Of Technology Windows implementing effectively transparent conductors and related methods of manufacturing
WO2020205800A1 (en) 2019-03-29 2020-10-08 California Institute Of Technology Apparatus and systems for incorporating effective transparent catalyst for photoelectrochemical application

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3497774A (en) * 1967-06-07 1970-02-24 Beckman Instruments Inc Electrical circuit module and method of manufacture
US4401767A (en) * 1981-08-03 1983-08-30 Johnson Matthey Inc. Silver-filled glass
US4459166A (en) * 1982-03-08 1984-07-10 Johnson Matthey Inc. Method of bonding an electronic device to a ceramic substrate
US4436785A (en) * 1982-03-08 1984-03-13 Johnson Matthey Inc. Silver-filled glass
US4636254A (en) * 1985-07-23 1987-01-13 Quantum Materials, Inc. Silver-glass paste for attachment of silicon die to ceramic substrate
US4636332A (en) * 1985-11-01 1987-01-13 E. I. Du Pont De Nemours And Company Thick film conductor composition
US4761224A (en) * 1986-03-10 1988-08-02 Quantum Materials Inc. Silver-glass paste with poly-modal flake size distribution and quick dry vehicle
US4881974A (en) * 1987-11-05 1989-11-21 Johnson Matthey, Inc. Silver-glass paste
GB8730196D0 (en) * 1987-12-24 1988-02-03 Johnson Matthey Plc Silver-filled glass
US4986849A (en) * 1988-09-23 1991-01-22 Johnson Matthey Inc. Silver-glass pastes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008192455A (en) * 2007-02-05 2008-08-21 Narumi China Corp Glass top plate for heating cooker
JP2012513683A (en) * 2008-12-23 2012-06-14 ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング Electrical or electronic composite component and method for manufacturing electrical or electronic composite component
JPWO2011158753A1 (en) * 2010-06-17 2013-08-19 日立化成株式会社 Resin paste composition

Also Published As

Publication number Publication date
EP0443842A1 (en) 1991-08-28
TW204333B (en) 1993-04-21
US5075262A (en) 1991-12-24
KR910021458A (en) 1991-12-20
CN1055164A (en) 1991-10-09

Similar Documents

Publication Publication Date Title
JPH056909A (en) Silver-glass paste
US5183784A (en) Silver-glass pastes
US2461878A (en) Metallizing composition
JP4355573B2 (en) Thermal melt conductor paste composition
US4859241A (en) Metal flake and use thereof
US5064480A (en) Water washable soldering paste
JP5323996B2 (en) Heat bonding material, heat bonding coating material, and coating
JPS5954496A (en) Brazing method and brazing paste
EP2425920A1 (en) Use of aliphatic hydrocarbons and paraffins as solvent in silver sintering pastes
JPH04224178A (en) Sealing glass composition
JPH01128488A (en) Thick film copper conductor ink
JPH0742138B2 (en) A paste for bonding semiconductors
JP2005504409A (en) Silver conductor composition
JPH01223738A (en) Silver-filled glass
US4986849A (en) Silver-glass pastes
US5240884A (en) Silver-glass die attach paste
US4369287A (en) Permanent fluxing agent and solder-through conformal coating
US4084314A (en) Producing thick film circuits having terminal elements
JPH01158790A (en) Silver-glass paste compound
US5084421A (en) Silver-glass pastes
CA1332177C (en) Oxide glasses having low glass transformation temperatures
US5164119A (en) Silver-glass pastes
JPH0337751B2 (en)
JP2561452B2 (en) Solder paste
JPS60140883A (en) Manufacture of semiconductor device